CN111491963B - Method for producing (meth)acrylic composition, paint and cured product containing (meth)acrylic composition - Google Patents

Abstract

The present invention provides a method for producing a (meth)acrylic composition that has a low viscosity, a high refractive index when cured, and less yellowing in an environmental test at high temperature and high humidity, and a method containing such a (meth)acrylic composition. Coatings of acrylic compositions. According to one embodiment, there is provided a method of mixing a (meth)acrylate of general formula (1) and a polyvalent (meth)acrylic monomer of general formula (2) within a predetermined temperature range.

Description

Method for producing (meth)acrylic acid composition, coating material containing (meth)acrylic acid composition and cured product

Technical Field

The present invention relates to a method for producing a (meth)acrylic composition, a coating material containing the (meth)acrylic composition, and a cured product of the composition.

Background Art

In recent years, from the perspective of excellent processing and productivity, resin materials are widely used in optical components such as optical outer coating agents, hard coating agents, anti-reflection films, eyeglass lenses, optical fibers, optical waveguides, holographic elements, etc. In addition, the trend of miniaturization and thinness in the field of optical components is rising, and with this, materials with high refractive index are required. In addition, in response to this requirement, coatings containing resin compositions with high refractive index when cured are widely used. On the other hand, such coatings usually have the feature of higher viscosity, so sometimes it is difficult to apply thinly. Therefore, a composition with low viscosity that is improved in this regard is proposed.

For example, Patent Document 1 proposes a high refractive index and low viscosity composition obtained by mixing o-phenylbenzyl acrylate (OPBA; or 2-phenylbenzyl acrylate) and p-phenylbenzyl acrylate (PPBA; or 4-phenylbenzyl acrylate), which are isomers of phenylbenzyl acrylate, at a specific ratio. In addition, Patent Document 2 describes a high refractive index and low viscosity composition obtained by mixing phenylbenzyl acrylate and a bifunctional (meth)acrylate or a diphenyl derivative.

Patent Documents 3 to 7 describe that a resin composition for an optical material is obtained by mixing phenoxybenzyl (meth)acrylate and a polyfunctional (meth)acrylate having a high refractive index (fluorene-based bisphenol derivative, bisphenol A derivative).

Prior art literature

Patent Literature

Patent Document 1: Japanese Patent Application Publication No. 2012-82387

Patent Document 2: Japanese Patent Application Publication No. 2012-82386

Patent Document 3: Japanese Patent Application Publication No. 2010-248358

Patent Document 4: Japanese Patent Application Publication No. 2011-126991

Patent Document 5: Japanese Patent Application Publication No. 2012-219205

Patent Document 6: Japanese Patent Application Publication No. 2013-53310

Patent Document 7: Japanese Patent Application Publication No. 2014-185337.

Summary of the invention

As described above, various compositions with high refractive index and low viscosity have been proposed so far. However, monofunctional (meth)acrylates with low viscosity often have low refractive index, and on the other hand, monofunctional (meth)acrylates with high refractive index sometimes cannot fully obtain the effect of reducing the viscosity of multifunctional (meth)acrylates with high refractive index. Based on such a situation, monofunctional (meth)acrylates with high refractive index and low viscosity have been developed. As an example, phenoxybenzyl (meth)acrylate represented by chemical formula (C) has been newly discovered and studied (for example, Patent Document 4, (B) component 1, etc.).

However, when phenoxybenzyl (meth)acrylate represented by the chemical formula (C) is used, the coating film is judged to be severely yellowed in an environmental test under high temperature and high humidity (specifically, 85°C/85%RH). Therefore, a (meth)acrylic composition having a low viscosity and a high refractive index when cured and having little yellowing in an environmental test under high temperature and high humidity is required.

The present invention has been made in view of such a problem, and its object is to provide a method for producing a (meth)acrylic composition having a low viscosity, a high refractive index when cured, and less yellowing in an environmental test under high temperature and high humidity, and a coating containing such a (meth)acrylic composition. In addition, the present invention aims to provide a cured product of the above composition.

The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by mixing a (meth)acrylate of the general formula (1) described below with a polyvalent (meth)acrylic monomer of the general formula (2) described below within a predetermined temperature range, thereby completing the present invention.

That is, the present invention has the following characteristics.

[1] A method for producing a liquid composition comprising (A) a (meth)acrylate ester represented by the following general formula (1) and (B) a polyvalent (meth)acrylic acid-based monomer represented by the following general formula (2),

[In formula (1),

X is a divalent group selected from a single bond, -C(R ₂ )(R ₃ )-, -C(═O)-, -O-, -OC(═O)-, -OC(═O)O-, -S-, -SO-, -SO ₂ -, and any combination thereof (wherein R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group, or a phenylphenyl group; or R ₂ and R ₃ may be linked to each other to form a cyclic alkyl group having 3 to 10 carbon atoms together with the carbon atoms to which they are linked);

Y is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;

_R1 is a hydrogen atom or a methyl group;

_R4 and _R5 are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group, or a phenylphenyl group;

m is an integer from 0 to 10;

n is an integer from 1 to 2;

p is an integer from 0 to 4;

q is an integer from 0 to 5]

[In formula (2),

_R10 and _R11 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,

R ₁₂ is a hydrogen atom or a methyl group;

X represents a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, or any of the following general formulae (3) to (6);

Y and Z are each independently an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;

p and q are each independently an integer of 0 to 4.]

[In formula (3),

_R13 and _R14 each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent;

The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

c represents an integer from 1 to 20. ]

[In formula (4), _R15 and _R16 each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or _R15 and _R16 each bond to each other to form a carbon ring or heterocyclic ring having 1 to 20 carbon atoms;

The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.]

[In formula (5), _R17 to _R20 each independently represent any one of a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or _R17 and _R18, and _R19 and _R20, respectively, are bonded to each other to form a carbon ring or heterocyclic ring having 1 to 20 carbon atoms;

The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.]

[In formula (6), R ₂₁ to R ₃₀ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.]

The above method includes the step of mixing the (meth)acrylate represented by the general formula (1) and the polyvalent (meth)acrylic monomer represented by the general formula (2) at a temperature of 35°C to 120°C.

[2]

According to the method described in [1], in the formula (1), p and q are both 0.

[3]

The method according to [1] or [2], wherein in the formula (1), n is 1 and m is 0.

[4]

The method according to any one of [1] to [3], wherein the content of the (meth)acrylate represented by the general formula (1) and the polyvalent (meth)acrylic monomer represented by the general formula (2) is 1:10 to 10:1 in a mass ratio.

[5]

The method according to any one of [1] to [4], wherein the (meth)acrylate represented by the general formula (1) is a blend of two or more compounds.

[6]

The method according to any one of [1] to [5], wherein in the formula (2), X has a structure represented by the general formula (4).

[7]

The method according to any one of [1] to [6], wherein the liquid composition is an active energy ray-curable composition.

[8]

A coating material comprising the composition obtained by the method according to any one of [1] to [7].

[9]

A cured product obtained by curing the composition obtained by the method according to any one of [1] to [7].

[10]

A method for manufacturing a solidified body, the method comprising:

A step of obtaining a composition using the method described in any one of [1] to [7]; and

The step of curing the composition.

According to the present invention, a method for producing a (meth)acrylic composition having a low viscosity, a high refractive index when cured, and less yellowing in an environmental test under high temperature and high humidity, and a coating containing such a (meth)acrylic composition can be provided. In addition, according to the present invention, a cured product of the above composition can also be provided.

DETAILED DESCRIPTION

Hereinafter, embodiments of the present invention will be described in detail.

＜Manufacturing method＞

The method for producing a liquid composition of the present invention is a method for producing a liquid composition containing (A) a (meth)acrylate represented by the following general formula (1) and (B) a polyvalent (meth)acrylic monomer represented by the following general formula (2).

[In formula (1),

X is a divalent group selected from a single bond, -C(R ₂ )(R ₃ )-, -C(═O)-, -O-, -OC(═O)-, -OC(═O)O-, -S-, -SO-, -SO ₂ -, and any combination thereof (wherein R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group, or a phenylphenyl group; or R ₂ and R ₃ may be linked to each other to form a cyclic alkyl group having 3 to 10 carbon atoms together with the carbon atoms to which they are linked);

Y is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;

_R1 is a hydrogen atom or a methyl group;

_R4 and _R5 are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group, or a phenylphenyl group;

m is an integer from 0 to 10;

n is an integer from 1 to 2;

p is an integer from 0 to 4;

q is an integer from 0 to 5]

[In formula (2),

_R10 and _R11 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,

R ₁₂ is a hydrogen atom or a methyl group;

X represents a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, or any of the following general formulae (3) to (6);

Y and Z are each independently an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;

p and q are each independently an integer of 0 to 4. ],

The above method includes the step of mixing the (meth)acrylate represented by the general formula (1) and the polyvalent (meth)acrylic monomer represented by the general formula (2) at a temperature of 35°C to 120°C.

As described above, the liquid composition obtained by mixing a (meth)acrylate having a structure of the general formula (1) and a polyvalent (meth)acrylic acid monomer having a structure of the general formula (2) within a predetermined temperature range has a low viscosity, a high refractive index when cured, and less yellowing in an environmental test under high temperature and high humidity. Although not limited by theory, the yellowing is presumed to be caused by a low glass transition temperature. In addition, it has been considered that the (meth)acrylate having a structure of the general formula (1) is usually solid at room temperature in many cases and cannot be used for the purpose of reducing the viscosity of the polyvalent (meth)acrylic acid monomer of the general formula (2) having a high refractive index and high viscosity. For example, Patent Document 1 considers that p-phenylbenzyl (meth)acrylate, which is one of the (meth)acrylates having a structure of the general formula (1), is solid at room temperature (mp: 32° C.), and therefore cannot be used for this purpose. In addition, in Patent Document 1, a liquid composition is obtained by mixing o-phenylbenzyl (meth)acrylate and p-phenylbenzyl (meth)acrylate, which are liquids at room temperature, in a specific ratio.

Under such circumstances, the present inventors have found that by heating the (meth)acrylate having the structure of the general formula (1) to a predetermined temperature range, the (meth)acrylate having the structure of the general formula (1) is liquefied, and in this state, mixed with a polyvalent (meth)acrylic monomer having the structure of the general formula (2), a liquid composition can be obtained. It was also surprisingly found that when the (meth)acrylate having the structure of the general formula (1) is liquefied and then mixed with a polyvalent (meth)acrylic monomer having the structure of the general formula (2), even if the obtained liquid composition is subsequently cooled, crystals and the like do not precipitate, and a stable liquid composition is obtained. Furthermore, the liquid composition thus obtained has a low viscosity, a high refractive index when cured, and little yellowing in an environmental test under high temperature and high humidity. The present invention was completed based on such findings.

The temperature at which the (meth)acrylate having the structure of the general formula (1) and the polyvalent (meth)acrylic monomer having the structure of the general formula (2) are mixed in the production method of the present invention is 35°C to 120°C, preferably 40°C to 100°C, and more preferably 45°C to 80°C. If the temperature during mixing is 35°C or higher, the (meth)acrylate having the structure of the general formula (1) is fully liquefied, and if it is 120°C or lower, polymerization of the monomers can be prevented. During mixing, at least the temperature of the (meth)acrylate having the structure of the general formula (1) may be adjusted to the above temperature range, and the polyvalent (meth)acrylic monomer having the structure of the general formula (2) may be directly mixed at room temperature.

The viscosity of the liquid composition of the present invention is less than 10,000 mPa·s, preferably 5,000 mPa·s or less, and more preferably 5 to 2,000 mPa·s, when measured at a measurement temperature of 25°C using an E-type viscometer (TV-22 model).

Hereinafter, each component contained in the composition obtained by the production method of the present invention will be described in order.

1. (Meth)acrylate

The (meth)acrylate used in the composition obtained by the production method of the present invention has a structure represented by the following general formula (1).

In formula (1), X is a divalent group selected from a single bond, -C(R ₂ )(R ₃ )-, -C(═O)-, -O-, -OC(═O)-, -OC(═O)O-, -S-, -SO-, -SO ₂ -, and any combination thereof, and is preferably a divalent group selected from a single bond, -C(R ₂ )(R ₃ )-, -O-, and any combination thereof. Here, R ₂ and R ₃ are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group, or a phenylphenyl group. Alternatively, _R2 and _R3 may be linked to each other to form, together with the carbon atoms to which they are linked, a cyclic alkyl group having 3 to 10 carbon atoms. Preferably, both _R2 and _R3 are hydrogen atoms.

Y is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.

_R1 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

_R4 and _R5 are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group, or a phenylphenyl group.

m is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably 0.

n is an integer of 1 to 2, and is preferably 1.

More preferably, n is 1 and m is 0.

p is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.

q is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0.

More preferably, both p and q are 0. When p and q are 0, it means that the hydrogen atoms of the benzene ring are not replaced by the functional groups of R ₄ and R ₅ .

Examples of the (meth)acrylate represented by the general formula (1) include 4-phenylbenzyl (meth)acrylate, 3-phenylbenzyl (meth)acrylate, 2-phenylbenzyl (meth)acrylate, 4-biphenylbenzyl (meth)acrylate, 3-biphenylbenzyl (meth)acrylate, 2-biphenylbenzyl (meth)acrylate, 4-benzylbenzyl (meth)acrylate, 3-benzylbenzyl (meth)acrylate, 2-benzylbenzyl (meth)acrylate, 4-phenethylbenzyl (meth)acrylate, 3-phenethylbenzyl (meth)acrylate, 2-phenethylbenzyl (meth)acrylate, 4-phenethylphenethyl (meth)acrylate, 3-phenethylphenethyl (meth)acrylate, 2-phenethylbenzyl (meth)acrylate, phenylethyl ester, 4-(4-methylphenyl)benzyl(meth)acrylate, 3-(4-methylphenyl)benzyl(meth)acrylate, 2-(4-methylphenyl)benzyl(meth)acrylate, 4-(4-methoxyphenyl)benzyl(meth)acrylate, 3-(4-methoxyphenyl)benzyl(meth)acrylate, 2-(4-methoxyphenyl)benzyl(meth)acrylate, 4-(4-bromophenyl)benzyl(meth)acrylate, 3-(4-bromophenyl)benzyl(meth)acrylate, 2-(4-bromophenyl)benzyl(meth)acrylate, 4-benzoylbenzyl(meth)acrylate, 3-benzoylbenzyl(meth)acrylate, 2-benzoylbenzyl(meth)acrylate, 4-(phenylsulfinyl)benzyl(meth)acrylate benzyl ester, 3-(phenylsulfinyl)benzyl (meth)acrylate, 2-(phenylsulfinyl)benzyl (meth)acrylate, 4-(phenylsulfonyl)benzyl (meth)acrylate, 3-(phenylsulfonyl)benzyl (meth)acrylate, 2-(phenylsulfonyl)benzyl (meth)acrylate, 4-((phenoxycarbonyl)oxy)benzyl (meth)acrylate, 3-((phenoxycarbonyl)oxy)benzyl (meth)acrylate, 2-((phenoxycarbonyl)oxy)benzyl (meth)acrylate, 4-(((meth)acryloyloxy)methyl)phenyl benzoate, 3-(((meth)acryloyloxy)methyl)phenyl benzoate, 2-(((meth)acryloyloxy)methyl)phenyl benzoate, phenyl 4-(((meth)acryloyloxy)methyl)phenyl benzoate ) acryloyloxy) methyl) benzoate, phenyl 3-(((meth) acryloyloxy) methyl) benzoate, phenyl 2-(((meth) acryloyloxy) methyl) benzoate, 4-(1-phenylcyclohexyl) benzyl (meth) acrylate, 3-(1-phenylcyclohexyl) benzyl (meth) acrylate, 2-(1-phenylcyclohexyl) benzyl (meth) acrylate, 4-phenoxybenzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, 4-(phenylthio) benzyl (meth) acrylate, 3-(phenylthio) benzyl (meth) acrylate, 2-(phenylthio) benzyl (meth) acrylate, and 3-methyl-4-(2-methylphenyl) benzyl methacrylate. These substances can be used alone or in combination of two or more. For example, the (meth)acrylate may be a blend of two or more compounds, in which case at least one methacrylate may be the (meth)acrylate represented by the above general formula (1). Among the above (meth)acrylates, 2-phenylbenzyl (meth)acrylate, 4-phenylbenzyl (meth)acrylate, 4-phenoxybenzyl (meth)acrylate and 4-benzylbenzyl (meth)acrylate are preferred, and 2-phenylbenzyl acrylate, 4-phenylbenzyl acrylate, 4-phenoxybenzyl acrylate and 4-benzylbenzyl acrylate are more preferred.

The amount of (meth)acrylate contained in the composition obtained by the manufacturing method of the present invention is not particularly limited within the scope of the present invention. The content of (meth)acrylate and the polyvalent (meth)acrylic monomer represented by the general formula (2) is preferably 1:9 to 9:1 in terms of mass ratio, more preferably 2:8 to 8:2, further preferably 3:7 to 7:3, and particularly preferably 4:6 to 6:4. In addition, it is preferred from the viewpoint that the higher the ratio of monofunctional (meth)acrylate, the more it can prevent peeling under high temperature and high humidity environments. Although not limited by theory, it is inferred that the reduced adhesion between the substrate and the cured body is due to the high water absorption rate.

3. Polyvalent (meth) acrylic monomers

The composition obtained by the production method of the present invention further contains a polyvalent (meth)acrylic monomer represented by the following general formula (2) which is copolymerizable with the (meth)acrylic acid ester represented by the above general formula (1).

In formula (2), _R10 and _R11 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom, and are preferably a hydrogen atom.

R ₁₂ is a hydrogen atom or a methyl group.

X represents a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, or any of the following general formulae (3) to (6).

Y and Z are each independently an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.

p and q are each independently an integer of 0 to 4, and preferably both p and q are 0.

In the following formula (3),

_R13 and _R14 each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, wherein each substituent is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferably, both _R13 and _R14 are hydrogen atoms.

c represents an integer of 1-20, preferably an integer of 1-10, and more preferably an integer of 1-5.

In the following formula (4),

R ₁₅ and R ₁₆ each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or R ₁₅ and R ₁₆ each bond to each other to form a carbon ring or heterocyclic ring having 1 to 20 carbon atoms, and the substituent each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferably, both R ₁₅ and R ₁₆ are hydrogen atoms.

In the following formula (5),

R ₁₇ to R ₂₀ each independently represent any one of a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or R ₁₇ and R ₁₈ , and R ₁₉ and R ₂₀ each bond to each other to form a carbon ring or heterocycle having 1 to 20 carbon atoms, and the substituent each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferably, R ₁₇ to R ₂₀ are all hydrogen atoms.

In the following formula (6),

R ₂₁ to R ₃₀ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Preferably, all of R ₂₁ to R ₃₀ are hydrogen atoms.

In the above formula (2), X preferably has a structure represented by the general formula (4).

Examples of the polyvalent (meth)acrylic monomer represented by the general formula (2) include 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 4,4′-isopropylidene diphenol di(meth)acrylate, 2,2′-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]propane, bis[4-(2-(meth)acryloyloxyethoxy)phenyl]methane, 1,1′-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]methane, bis[4-(2-(meth)acryloyloxyethoxy)phenyl]ether, bis[4-(2-(meth)acryloyloxyethoxy)phenyl]sulfoxide, bis[4-(2-(meth)acryloyloxyethoxy)phenyl]sulfide, bis(4-(2-(meth)acryloyloxyethoxy)phenyl]sulfone, bis(4-(2-(meth)acryloyloxyethoxy)phenyl]sulfone, and bis(4-(2-(meth)acryloyloxyethoxy)phenyl]sulfone. )acryloyloxyethoxy)phenyl] ketone, ethoxylated bisphenol A diacrylate, and 4,4'-di(meth)acryloyloxybiphenyl, etc. Among them, preferred are 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 4,4'-isopropylidene diphenol di(meth)acrylate, ethoxylated bisphenol A diacrylate, and 2,2'-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]propane, and more preferred are ethoxylated bisphenol A diacrylate and 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene. In addition, commercially available products of the polyvalent (meth)acrylic monomer represented by the general formula (2) include, for example, ABE-300, A-BPE-4, and A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd., and LIGHT manufactured by Kyoeisha Chemical Co., Ltd. ACRYLATE BP-4EAL, VISCOAT#700HV manufactured by Shin-Nakamura Chemical Co., Ltd., FA-324A manufactured by Hitachi Chemical Co., Ltd., etc., but are not limited to these.

3. Any additives

The composition obtained by the manufacturing method of the present invention may contain various arbitrary additives according to the purpose in addition to the above-mentioned constituent components within the scope of not departing from the main purpose of the present invention. As such additives, at least one additive selected from a heat stabilizer, an antioxidant, a flame retardant, a flame retardant aid, an ultraviolet absorber, a release agent and a colorant can be exemplified. The amount of the additive is preferably 0.005 to 0.1 parts by mass, more preferably 0.01 to 0.05 parts by mass, relative to a total of 100 parts by mass of the (meth)acrylate represented by the general formula (1) and the polyvalent (meth) acrylic monomer represented by the general formula (2).

The composition obtained by the method of the present invention can be cured by various methods. The details will be described later, but the composition obtained by the method of the present invention is preferably an active energy ray-curable composition.

＜Paint＞

The coating material of the present invention comprises the composition obtained by the method of the present invention. The coating material of the present invention can be used mainly as a coating agent, a hard coating agent, etc. for optical parts.

When the coating of the present invention is applied to a general substrate such as plastic, a wetting agent such as a silicone or acrylic compound may be added to the coating to help wet the surface of the various substrates. Suitable wetting agents include BYK331, BYK333, BYK340, BYK347, BYK348, BYK378, BYK380, BYK381, etc. available from BYK Chemie. When these are added, the amount is preferably in the range of 0.01 to 2.0% by mass based on the total mass of the coating.

In order to improve the adhesion to various materials, adhesion agents such as xylene resin, terpene resin, phenolic resin, rosin resin, etc. can be added to the coating as needed. When adding these, the range of 0.01 to 2.0 mass % based on the total mass of the coating is preferred.

In order to improve the adhesion to various materials, a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the coating material. When such a coupling agent is added, the amount thereof is preferably in the range of 0.01 to 5.0% by mass based on the total mass of the coating material.

In order to improve various properties such as impact resistance, inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes may be added to the coating. When these are added, the amount is preferably in the range of 0.01 to 10.0% by mass based on the total mass of the coating.

Furthermore, when the coating of the present invention is applied to a general substrate such as metal, concrete, or plastic, a defoamer composed of a silicone or acrylic compound may be added to the coating in order to help eliminate bubbles generated during mixing and application. Suitable defoamers are preferably BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070N, BYK080, etc. available from BYK Chemie, and BYK065 is particularly preferred. When these defoamers are added, the amount is preferably in the range of 0.01 to 3.0% by mass based on the total mass of the coating.

To the coating of the present invention, necessary amounts of various components such as zinc phosphate, iron phosphate, calcium molybdate, vanadium oxide, water-dispersible silica, fumed silica and other rust-inhibiting additives, organic pigments such as phthalocyanine organic pigments and condensed polycyclic organic pigments, and inorganic pigments such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, aluminum oxide, and carbon black can be added as needed.

As the coating method when the coating of the present invention is applied to various substrates, any of the generally used coating methods such as rod coating, Mayer rod coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coating, die coating, slot die coating, vacuum die coating, dip coating, spin coating, spray coating, brush coating, etc. can be used. Roll coating and spray coating are preferred.

＜Solidified body＞

The cured product of the present invention is a cured product obtained by curing the composition obtained by the method of the present invention. The cured product of the present invention has a high refractive index of more than 1.580, and yellowing is less in environmental tests under high temperature and high humidity. In addition, the cured product of the present invention preferably has a high refractive index of more than 1.585, and more preferably has a high refractive index of more than 1.590. And, the cured product of the present invention preferably has a yellowness (YI) of less than 4.0 when stored in an atmosphere of 85°C/85%RH for 350 hours. Preferably, the yellowness (YI) is less than 6.5 when stored in an atmosphere of 85°C/85%RH for 1000 hours.

The cured product of the present invention contains (A) a structural unit derived from a (meth)acrylate ester represented by the general formula (1) and a structural unit derived from a polyvalent (meth)acrylic monomer represented by the general formula (2).

X, Y, _R1 , _R4 , _R5 , m, n, p and q in general formula (1) are the same as those in the composition obtained by the method of the present invention. _R10 , _R11 , _R12 , X, Y, Z, p and q in general formula (2) are also the same as those in the composition obtained by the method of the present invention.

The structural unit derived from (meth)acrylate represented by the general formula (1) means a structural unit having a structure of the following formula (1a):

The structural unit derived from a polyvalent (meth)acrylic monomer represented by the general formula (2) means a structural unit having a structure represented by the following formula (2a).

Here, X, Y, R ₁ , R ₄ , R ₅ , m, n, p and q in general formula (1a) correspond to general formula (1), respectively, and R ₁₀ , R ₁₁ , R ₁₂ , X, Y, Z, p and q in general formula (2a) correspond to general formula (2), respectively.

The manufacturing method of the cured body of the present invention comprises the process of obtaining the composition by the method of the present invention and the process of curing the composition. Here, the method for curing is not particularly limited and can be carried out by various known methods. For example, the composition of the present invention can be cured by photopolymerization based on irradiation of active energy rays. In this specification, "active energy rays" refers to ultraviolet rays, electron beams, ion beams, and X-rays, etc.

When the composition obtained by the method of the present invention is cured by active energy rays, a photopolymerization initiator is not necessarily required. However, when a photopolymerization initiator is added, examples thereof include Irgacure (registered trademark) 2959 (1-[4-(2-hydroxyethoxy)phenyl)]-2-hydroxy-2-methyl-1-propane-1-one, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ket ... )651 (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1), Irgacure (registered trademark) 907 (2-methyl-1 [4-methylthiophenyl]-2-morpholinopropane-1-one), Irgacure (registered trademark) 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), Irgacure (registered trademark) 1,2-dimethyl-2-(4-morpholinophenyl)butanone-1-one), Irgacure (registered trademark) 2-methyl-1 [4-methylthiophenyl] -2-morpholinopropane-1-one), Irgacure (registered trademark) 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), Irgacure (registered trademark) 1,2-dimethyl-2-(4-morpholinophenyl)butanone-1-one), Irgacure (registered trademark) 1,2-dimethyl-2-(4-methylthiophenyl) -2-morpholinopropane ... cure (registered trademark) 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure (registered trademark) 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propane-1-one), Irgacure (registered trademark) OXEO1 (1,2-octanediol), 1-[ 4-(phenylthio)phenyl]-2-(O-benzoyl oxime), Darocur (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242 (ethane, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime)), Lucirin available from BASF TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO-L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE1001M (1-[4-benzoylphenylsulfanyl]phenyl)-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one available from Japan SiberHegner Co., Ltd., ADEKA OPTOMER (registered trademark) N-1414 (carbazole·benzophenone series) available from Asahi Denka Co., Ltd., ADEKA OPTOMER (registered trademark) N-1717 (acridine series), ADEKA OPTOMER (registered trademark) N-1606 (triazine series), TFE-triazine (2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine) manufactured by Sanwa Chemical, TME-triazine (2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine) manufactured by Sanwa Chemical, MP-triazine (2-[2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine) manufactured by Sanwa Chemical, TAZ-113 (2-[2-(3,4-dimethoxyphenyl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine) manufactured by Midori Kagaku, Kagaku TAZ-108 (2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, Diethoxyacetophenone and dibenzosuberone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, 1,4-benzoylbenzene, benzil, 10-butyl-2-chloroacridone, [4-(methylphenylthio)phenyl]phenylmethane), 2-ethylanthraquinone, 2,2-bis(2-chlorophenyl)4,5,4',5'-tetrakis(3,4,5-trimethoxyphenyl)1,2'-biimidazole, 2,2-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-biimidazole, tris(4-dimethylaminophenyl)methane, ethyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, butoxyethyl-4-(dimethylamino)benzoate, etc. These photopolymerization initiators may be used alone or in combination of two or more. The amount of these photopolymerization initiators added is in the range of 0.01% by mass to 15% by mass, preferably 0.1% by mass to 10% by mass in the composition.

Hereinafter, the present invention will be described in detail with reference to Examples, but the technical scope of the present invention is not limited thereto. "Parts" and "%" in the Examples represent "parts by mass" and "mass %", respectively.

In addition, the measurement of each physical property of Examples and Comparative Examples was carried out according to the following methods.

1. Viscosity of the composition

The viscosity of the composition obtained by the method described below was measured at a measurement temperature of 25°C using an E-type viscometer (TV-22 model).

2. Refractive index of the composition

The composition obtained by the method described below was measured at a measurement wavelength of 589 nm and a measurement temperature of 23° C. using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.).

3. Refractive index of the cured product

The cured product of the composition obtained by the method described below was measured at a measurement wavelength of 589 nm and a measurement temperature of 23° C. using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.).

4. Yellowness (YI)

The yellowness (YI) was measured in accordance with JIS K 7373 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries, Ltd.).

5. Peelability

The cured product of the composition obtained by the method described below was stored in an environment of 85° C. and 85% RH. After a predetermined period of time had passed, it was visually confirmed whether the cured product of the composition was peeled off from the PET film as the substrate film.

<Example 1: Preparation of the composition and its cured product>

In order to examine the viscosity and refractive index of a liquid composition containing a monofunctional (meth)acrylate and a polyvalent (meth)acrylic monomer represented by the general formula (2), liquid composition examples 1 to 3 were prepared with the compositions shown in Table 1. The polyvalent (meth)acrylic monomer represented by the general formula (2) whose viscosity is reduced by heating at 60°C for 1 hour and the monofunctional (meth)acrylate were blended and stirred well to uniformly dissolve to obtain a liquid composition. Then, the composition was stored at 23°C for 12 hours to set the temperature of the composition to 23°C. Thereafter, the viscosity and refractive index were measured.

[Table 1]

Table 1

As the compounds of chemical formulae (A) to (D), the following compounds were used. As the compound of chemical formula (A), OGSOL EA0200 manufactured by Osaka Gas Chemical Co., Ltd. was used, as the compound of chemical formula (B), ALEN-10 manufactured by Shin-Nakamura Chemical Co., Ltd. was used, as the compound of chemical formula (C), POB-A manufactured by Kyoeisha Chemical Co., Ltd. was used, and the compound of chemical formula (D) was synthesized according to a known method.

The synthesis method of the compound of chemical formula (D) is as follows. First, 90 parts by weight of biphenylmethanol, 156 parts by weight of methyl acrylate, and 0.4 parts by weight of 4-methoxyphenol are placed in a round-bottom flask, and after heating to remove the moisture in the system under air circulation, 0.82 parts by weight of titanium tetraisopropoxide are added to start the reaction. The reaction solution is heated to 90°C, the methanol generated by the reaction is removed, and the reaction is carried out for 6 hours while methyl acrylate is appropriately added. After the reaction is completed, the catalyst is hydrolyzed by adding 10 parts by weight of pure water. Then, it is purified by distillation and filtration to obtain a compound of chemical formula (D).

From the above results, it can be seen that when the compound of the chemical formula (D) is used, a liquid composition having a low viscosity and a high refractive index when cured is obtained.

<Example 2: Physical properties of each liquid composition and its solidified body>

Liquid composition examples 14 to 16 containing a monofunctional (meth)acrylate and a polyvalent (meth)acrylic monomer represented by the general formula (2) in a ratio of 50:50 were prepared, and the physical properties of the compositions and cured products were measured. 20 parts by mass of a polyvalent (meth)acrylic monomer represented by the general formula (2) whose viscosity is reduced by heating at 60°C for 1 hour, 20 parts by mass of a monofunctional (meth)acrylate, and 1.2 parts by mass of Irugacure 184 (manufactured by Ciba Speciality Chemicals) as a photopolymerization initiator were blended, stirred well, and uniformly dissolved to obtain a liquid composition. Next, the liquid composition was applied to the corona-treated surface of a polyester film (manufactured by Toyobo Co., Ltd.; Toyobo Ester Film E5100) having a thickness of 50 μm as a substrate using a rod coater No. 60, and then immediately irradiated with ultraviolet light using a conveyor- ^type ultraviolet irradiation device U-0303 (manufactured by GS Yuasa Co., Ltd., using a high-pressure mercury lamp, lamp output: 80 W/cm, conveyor speed: 4.8 m/min) set to an ultraviolet irradiation amount of 300 mJ/cm2 to obtain a film having a cured body of the liquid composition formed on the polyester film. The results are shown in Table 2.

[Table 2]

Table 2

The physical properties described in Table 2 were measured by the following methods.

[Pencil hardness]

The pencil hardness is measured in accordance with JIS K5600-5-4. Specifically, a pencil is pressed against the surface of the polyester film on which the cured body of the liquid composition is formed, at an angle of 45 degrees and a load of 750 g, in order from the hardest side to the dry coating surface, and the hardness of the hardest pencil that does not produce scratches is evaluated as the pencil hardness. The order of pencil hardness from low to high is expressed as: 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H and 7H.

[Elongation]

20 parts by mass of a polyvalent (meth)acrylic monomer represented by the general formula (2) whose viscosity is reduced by heating at 60°C for 1 hour, 20 parts by mass of a monofunctional (meth)acrylate, and 1.2 parts by mass of Irugacure 184 (manufactured by Ciba Speciality Chemicals) as a photopolymerization initiator were mixed and stirred well to uniformly dissolve to obtain a liquid composition. Next, the liquid composition was applied to the corona-treated surface of a 50 μm thick polyester film (manufactured by Toyobo Co., Ltd.; Toyobo Ester Film E5100) as a substrate using a bar coater No. 60, and then immediately irradiated with ultraviolet rays using a conveyor- ^type ultraviolet irradiation device U-0303 (manufactured by GS Yuasa Co., Ltd., using a high-pressure mercury lamp, lamp output: 80 W/cm, conveyor speed: 4.8 m/min) set to an ultraviolet irradiation dose of 300 mJ/cm2 to obtain a film having a cured body of the liquid composition formed on the polyester film. The cured product of the liquid composition was peeled off from the polyester film surface, and a tensile test was performed in accordance with JIS K 7161-1.

[Haze]

The haze was measured in accordance with JIS K 7136 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries, Ltd.).

[Total light transmittance]

The total light transmittance (T.T.) was measured in accordance with JIS K 7375 using a haze meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[Saturated water absorption]

The solidified body of the liquid composition was prepared as described above, and a 5 cm × 5 cm sample piece was prepared, which was dried at 50°C for 24 hours. The weight of the dried sample was then measured, and then the sample was immersed in water at 23°C. After a predetermined time, the sample was taken out of the water, the water was wiped off, and its mass was measured. This operation was continued until the water absorption reached saturation, and the weight of the saturated sample was taken as the weight at saturation, and the saturated water absorption was measured according to the following calculation formula.

Saturated water absorption (%) = weight of test piece at saturation / weight of dried sample × 100

[Glass transition temperature]

The glass transition temperature was measured using DSC6200 (manufactured by Seiko Instruments Co., Ltd.) in accordance with JIS-K-7121.

From the above results, it is understood that when the monofunctional (meth)acrylate of the chemical formula (D) is used, a cured product having a high refractive index, a low water absorption rate, and a high Tg can be obtained.

<Example 3: Coloration Evaluation of Each Liquid Composition and Its Cured Body at High Temperature and High Humidity>

Liquid composition examples 17 to 25 containing a monofunctional (meth)acrylate and a polyvalent (meth)acrylic monomer represented by the general formula (2) in the ratios described in Table 3 were prepared, and the coloration of each under high temperature and high humidity was evaluated. During the preparation, the polyvalent (meth)acrylic monomer represented by the general formula (2) whose viscosity was reduced by heating at 600°C for 1 hour was mixed with the monofunctional methacrylate in the ratio described in Table 3. In addition, the occurrence of peeling under high temperature and high humidity was also confirmed. A polyester film having a cured body formed with the liquid composition was stored in a constant temperature and humidity machine set to an atmosphere of 85°C/85%RH, and the yellowness (YI) was measured according to the above-mentioned measurement method after 350 hours and 1000 hours.

[Table 3]

Table 3

The above results show that the use of the monofunctional (meth)acrylate of the chemical formula (D) can suppress coloring even under high temperature and high humidity conditions, and that the addition amount of the monofunctional methacrylate to 75 wt % can effectively suppress peeling.

<Example 4: Evaluation of crystallization>

Liquid composition examples 26 to 49 containing a monofunctional (meth)acrylate and a polyvalent (meth)acrylic monomer represented by the general formula (2) in the ratios described in Tables 4 to 6 were prepared, and whether the occurrence of crystallization was affected by changing the blending temperature at this time was evaluated. The results are shown in Tables 4 to 7. The compounds of the chemical formulas (A), (C), and (D) adjusted to the temperature shown in the table were blended using the formulation and method shown in the table, stirred well, and dissolved uniformly to obtain a liquid composition. In addition, the chemical formula (D)/(C) refers to a mixture in which the weight ratio of the compound of the chemical formula (D) to the compound of the chemical formula (C) is 1:1. Then, the mixture was stored under the storage conditions shown in the table, and after a predetermined time, the presence or absence of crystal precipitation was visually confirmed. In addition, "23°C/1 day → 5°C storage" means storage at 5°C after storage at 23°C for 1 day, and "crystallization (5°C/5 days)" means storage at 5°C for 5 days.

[Table 4]

Table 4

The results of Examples 26 and 27 show that setting the blending temperature to 40°C has an effect of suppressing crystallization more than the case of blending at 23°C.

[Table 5]

[Table 6]

Table 6

[Table 7]

Table 7

According to the above results, by setting the blending temperature to 60°C, crystallization is further suppressed, and no crystals are produced in the liquid composition after storage for more than 5°C/30 days. In addition, even if only the monofunctional (meth)acrylate is heated to 60°C, no crystals are produced when the obtained liquid composition is stored for more than 5°C/30 days. Moreover, as a compound of chemical formula (A), the same results can be obtained even when A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd. is used. In addition, when blending at a temperature exceeding 120°C, the (meth)acrylate of the monomer may polymerize, so the test is terminated at 120°C.

<Example 5: Solubility of the Crystallized Polyvalent (Meth) Acrylic Monomer Represented by General Formula (2)>

In the case where the polyvalent (meth)acrylic monomer represented by the general formula (2) has already crystallized before being blended with the monofunctional (meth)acrylate, whether the crystals are dissolved by blending with the heated monofunctional (meth)acrylate was evaluated. At this time, after the monofunctional (meth)acrylate and the polyvalent (meth)acrylic monomer were mixed at various blending temperatures and then kept at 60°C, whether the crystallized polyvalent (meth)acrylic monomer was dissolved was evaluated. The results are shown in Table 8. In addition, "Solubility (60°C/N days)" in the table refers to the degree of dissolution when stored at 60°C for N days.

[Table 8]

Table 8

The above results show that the use of the monofunctional (meth)acrylate of the chemical formula (D) allows the polyvalent (meth)acrylic monomer represented by the general formula (2) to be well dissolved even when it is crystallized.

Claims (9)

1. A method for producing a liquid composition comprising (A) a (meth) acrylic acid ester represented by the following general formula (1) and (B) a polyvalent (meth) acrylic monomer represented by the following general formula (2),

in the formula (1), the amino acid sequence of the formula (1),

x is selected from single bond, -C (R) ₂ )(R ₃ )－、－C(＝O)－、－OC(＝O)－、－OC(＝O)O－、－S－、－SO－、－SO ₂ Divalent radicals in any combination thereof, where R ₂ And R is ₃ Each independently represents a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 1 to 10 carbon atoms10, a linear alkoxy group having 3 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group, or a phenylphenyl group; alternatively, R ₂ And R is ₃ Can be linked to each other to form a cyclic alkyl group having 3 to 10 carbon atoms together with the carbon atoms to which they are bonded;

y is an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, which may be branched;

R ₁ Is a hydrogen atom or a methyl group;

R ₄ and R is ₅ Each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group, or a phenyl group;

m is an integer of 0 to 10;

n is an integer of 1 to 2;

p is an integer of 0 to 4;

q is an integer of 0 to 5,

in the formula (2), the amino acid sequence of the formula (2),

R ₁₀ and R is ₁₁ Each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,

R ₁₂ is a hydrogen atom or a methyl group;

x represents a single bond, -O-, -S-, -SO ₂ -, -CO-and any one of the structures of the following general formulae (3) to (6);

y and Z are each independently a branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms;

p and q are each independently integers from 0 to 4,

in the formula (3), the amino acid sequence of the compound,

R ₁₃ And R is ₁₄ Each independently represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent;

each of the substituents is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

c represents an integer of 1 to 20,

in formula (4), R ₁₅ And R is ₁₆ Each independently represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or R ₁₅ And R is ₁₆ Each of which is bonded to each other to form a carbon ring or a heterocyclic ring having 1 to 20 carbon atoms;

each of the substituents is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms,

In formula (5), R ₁₇ ～R ₂₀ Each independently represents any one of a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or R ₁₇ And R is ₁₈ R is as follows ₁₉ And R is ₂₀ Respectively bonding to form carbocycle or heterocycle with 1-20 carbon atoms;

each of the substituents is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms,

in formula (6), R ₂₁ ～R ₃₀ Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

the method comprises a step of mixing the (meth) acrylate represented by the general formula (1) with the polyvalent (meth) acrylic monomer represented by the general formula (2) at a temperature of 35 to 120 ℃,

the content of the (meth) acrylic acid ester represented by the general formula (1) and the polyvalent (meth) acrylic monomer represented by the general formula (2) is 2 in terms of mass ratio: 8-8: 2.

2. the method according to claim 1, wherein in the formula (1), p and q are each 0.

3. The method according to claim 1 or 2, wherein in the formula (1), n is 1 and m is 0.

4. The method according to claim 1 or 2, wherein the (meth) acrylate represented by the general formula (1) is a blend of two or more compounds.

5. The method according to claim 1 or 2, wherein in the formula (2), X has a structure represented by the general formula (4).

6. The method according to claim 1 or 2, wherein the liquid composition is an active energy ray curable composition.

7. A coating comprising the composition obtained by the method according to any one of claims 1 to 6.

8. A cured product obtained by curing the composition obtained by the method according to any one of claims 1 to 6.

9. A method for producing a cured body, the method comprising:

a step of obtaining a composition by the method according to any one of claims 1 to 6; and

and a step of curing the composition.